EP3353836A1 - Electrochemical reactor block - Google Patents

Electrochemical reactor block

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Publication number
EP3353836A1
EP3353836A1 EP16777723.4A EP16777723A EP3353836A1 EP 3353836 A1 EP3353836 A1 EP 3353836A1 EP 16777723 A EP16777723 A EP 16777723A EP 3353836 A1 EP3353836 A1 EP 3353836A1
Authority
EP
European Patent Office
Prior art keywords
chains
linear polymer
group
carbon nanotubes
pellets
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16777723.4A
Other languages
German (de)
French (fr)
Other versions
EP3353836B1 (en
Inventor
Serge Cosnier
Raoudha HADDAD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universite Grenoble Alpes
Original Assignee
Universite Grenoble Alpes
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universite Grenoble Alpes filed Critical Universite Grenoble Alpes
Publication of EP3353836A1 publication Critical patent/EP3353836A1/en
Application granted granted Critical
Publication of EP3353836B1 publication Critical patent/EP3353836B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8626—Porous electrodes characterised by the form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method of manufacturing a block of an electrochemical reactor at which a reaction between catalytic agents confined in this reactor and compounds present in a liquid medium in which the reactor bathes is likely to occur.
  • This reaction may for example lead to a deformation of the reactor, to the generation of an electrical potential, or to the chemical transformation of the compound interacting with the reactor.
  • This reactor can be a bioreactor.
  • a bioreactor leading to the generation of an electrical potential may constitute a bioelectrode of a biopile or a biosensor, of the sugar-oxygen type, for example glucose-oxygen.
  • a bioreactor leading to the chemical transformation of a compound interacting with the bioreactor constitutes, for example, a glucose killer by transforming, for example, glucose into a compound that will be eliminated, for example, by the organism in which the bioreactor is implanted.
  • a glucose killer by transforming, for example, glucose into a compound that will be eliminated, for example, by the organism in which the bioreactor is implanted.
  • the invention and the state of the art are described here mainly in the case of bioelectrodes it will be understood that the invention is applicable to any electrochemical reactor, and not only to an implantable bioreactor in vivo. Presentation of the prior art
  • an embodiment provides a method of manufacturing an electrochemical reactor block comprising the following steps: producing a flexible conductive film comprising chains of a linear polymer to each of which are bonded by pi-pi interaction of carbon nanotubes;
  • the step of producing a flexible conductive film comprises the following steps:
  • the catalyst is selected from the group consisting of enzymes, metal catalysts, macrocyclic catalysts, and redox mediators.
  • the linear polymer is chosen from the group comprising polynorbornenes, polyvinylpyrrolidone and sodium polystyrene sulphonate.
  • each of said functional groups comprising a conjugated pi group is chosen from the group comprising porphyrins, phthalocyanine, pyrene, benzene, indole, azulene, phenothiazines and naphthalene.
  • a distance smaller than the length of the nanotubes separates two successive conjugated pi groups from the same linear polymer chain.
  • the length of each of said polymer chains is greater than 0.1 ⁇ m.
  • One embodiment provides an electrochemical reactor block comprising at least two pellets cut from a flexible conductive film comprising chains of a linear polymer each of which is bonded by pi-pi interaction of carbon nanotubes, a catalyst selected from the group consisting of enzymes, metal catalysts, macrocyclic catalysts and mediators redox being trapped between the pellets.
  • the electrochemical reactor block constitutes the cathode of a biopile intended to be immersed in a liquid medium containing a sugar and oxygen, and the catalyst is laccase.
  • the electrochemical reactor block constitutes the anode of a biopile intended to be immersed in a liquid medium containing a sugar and oxygen, and the catalyst agent is glucose oxidase.
  • FIGS. 1A to 1C schematically illustrate steps of an embodiment of a method of manufacturing a flexible conductive film
  • FIG. 2 schematically illustrates the structure of a flexible conductive film made according to the method of FIGS. 1A to 1C;
  • Figure 4 shows an embodiment of a stack of pellets cut in a film.
  • FIGS. 1A to 1C schematically illustrate successive steps of an embodiment of a flexible conductive film.
  • a suspension comprising, in a solvent 22, carbon nanotubes 24 and chains 26 of a linear polymer was prepared.
  • the solvent 22 is hydrophobic.
  • the solvent may be chosen from the group comprising dimethylformamide (DMF), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dichloromethane, nitrobenzene and chloroform.
  • Each channel 26 of the linear polymer carries a succession of functional groups 28 having group ⁇ ments conjugated pi 30.
  • the carbon nanotubes 24 are conductive because of the electron mobility of the moieties conjugated pi carbon nanotubes.
  • a conjugated pi group of a chain 26 of the linear polymer can bind pi-pi interaction (pi-stacking) to a conjugated pi moiety of a carbon nanotube 24.
  • the carbon nanotubes 24 are single or multi-layer nanotubes and may have a length of between 100 nm and 5 ⁇ m.
  • Each functional group 28 comprising a conjugated pi group 30 is for example a macrocycle such as porphyrins and phthalocyanine, or an aromatic compound such as pyrene, benzene, indole, azulene, phenothiazines or naphthalene.
  • the linear polymer may be selected from the group consisting of polynorbornenes, polyvinylpyrrolidone (PVP) and sodium polystyrene sulfonate (PSS).
  • PVP polyvinylpyrrolidone
  • PSS sodium polystyrene sulfonate
  • the distance between two successive conjugated pi groups of the same chain 26 is less than the length of the carbon nanotubes 24.
  • This distance is for example between 5 and 50 nm for nanotubes with a length of 200 to 500 nm.
  • the length of the chains 26 of the linear polymer is chosen to carry a plurality of functional groups 28, for example at least three functional groups 28, and preferably at least 50 groups.
  • the length of a chain may be greater than 0.1 ⁇ m, preferably greater than 10 ⁇ m.
  • the weight of all the carbon nanotubes 24 in the suspension 20 is, for example, from 0.1 to 10 times, preferably 3 to 6 times the weight of all the chains 26 of the linear polymer.
  • the suspension 20 is vacuum filtered through a membrane 32, for example a PTFE (PolyTetrafluoroethylene) membrane, comprising pores 34 whose diameter is for example between 0.1 and 0, 5 ym.
  • a membrane 32 for example a PTFE (PolyTetrafluoroethylene) membrane, comprising pores 34 whose diameter is for example between 0.1 and 0, 5 ym.
  • the chains 26 of the linear polymer to which carbon nanotubes 24 are bonded then accumulate in a film on the surface of the membrane 32.
  • a film 36 is obtained comprising carbon nanotubes bonded to the linear polymer chains.
  • the thickness of the film 36 is between 0.01 and 1 mm.
  • the surface concentration of carbon nanotubes may be 3.4 mg / cm 2 and that of the linear polymer chains may be 0.56 mg / cm 2.
  • FIG. 2 is a pictorial representation of the chains
  • the carbon nanotubes 24 are linked by pi-pi interaction with conjugated pI groups of the functional groups 28 carried by the chains 26 of the linear polymer.
  • a chain 26 carries several nanotubes 24 and each nanotube can be linked to several chains.
  • pellets 37 It is proposed here to cut into this film, which has for example a diameter of the order of 10 to 50 centimeters and a thickness of the order of 100 to 300 ⁇ m, pellets 37. Then, a reactor block 40 is produced. by stacking several of these pellets, for example three in the example shown, and subjecting them to a pressure, for example of the order of 5 to 10 tons per square centimeter. An extremely rigid block is then obtained, provided that the pressurization has been carried out while a few drops of water are inserted between each pellet, and between each pellet and the pressing plates of the press. Then, the block is easily detached from the press and does not tear or disintegrate. This strength is attributed to the interaction between the pi-pi bonds of the polymer of a pellet and the carbon nanotubes of the adjacent pellet.
  • This block is functionalized by inserting between the pellets during the pressurization an aqueous solution containing a suitable catalyst.
  • the suitable catalyst agent is trapped (trapped) between the pellets and a rigid block is obtained which is unlikely to disintegrate and the catalyst agent is immobilized and not likely to escape into the solution in which the block is disposed.
  • This compres ⁇ sion and pi-pi bonds between disks resulting catalysts allow imprisoning agents placed between the discs. It may further establish a covalent or non-covalent bond between these catalysts and the discs which further improves the trapping of the catalyst agents.
  • the intercalated catalyst agents may be enzymes and / or redox mediators, metal or macrocyclic catalysts or metal nanoparticles, oxides or organometallic complexes. All these compounds catalyze a reaction and thus a reactor was realized and, if there is an electrochemical reaction, it is an electrochemical reactor.
  • the chains of the linear polymer may carry functional groups capable of binding to an enzyme in addition to functional groups comprising conjugated pi groups.
  • the functional group may be a biotin.
  • the functional group may be an N-hydroxysuccinimide which reacts with the amino groups of the enzymes, thereby creating a covalent bond between the film and the enzyme.
  • bifunctional molecules each of which bears, on the one hand, a functional group comprising a conjugated pi group capable of binding to a flexible conductive film element, and, on the other hand, a functional group. able to bind to an enzyme.
  • the film can be specialized with functional groups capable of binding to an oxidation-reduction mediator.
  • the chains of the linear polymer carry functional groups capable of binding to the redox mediator.
  • the functional groups capable of binding to the redox mediator it will also be possible for the functional groups capable of binding to the redox mediator to be carried by bifunctional molecules, having on the one hand a functional group making it possible to bind to the redox mediator and on the other hand a pivotal group. conjugate allowing the binding with the carbon nanotubes or that the oxidation-reduction mediator is functionalized by a functional group capable of binding directly on the carbon nanotubes.
  • the film comprises functional groups comprising activated esters such as the reactive N-hydroxysuccinimide with the amino motif of toluidine blue.
  • the oxidation-reduction mediator can also be viologen, in which case viologen is expected to be functionalized by a pi-conjugated group such as pyrene, the viologen will then be attached to the film by pi-pi interaction between a carbon nanotube. and the conjugated pi moiety of the functionalized viologen.
  • Examples 1 to 4 below are examples of electrochemical reactors comprising catalyst agents trapped between linear polymer films and carbon nanotubes.
  • the catalyst agent trapped between the pellets is an enzyme such as laccase.
  • the system once immersed in an aqueous solution, for example in a human or animal body, functions as a cathode and a positive potential appears on a contact formed on an upper pellet.
  • a biopile is made using an anode block and a cathode block.
  • the anode block catalyst comprises, for example, glucose oxidase plus a redox mediator and the catalyst of the cathode block comprises, for example, laccase.
  • This biopile is small in size and is implantable in vivo.
  • Rhodium porphyrin acts to oxidize glucose and cobalt phthalocyanine to reduce oxygen. It should be noted that this reaction only works when the two blocks are immersed in a high pH solution, which constitutes a non-implantable cell in vivo.
  • the catalyst inserted between the pellets consists of platinum nanoparticles.
  • blocks comprising a single enzyme and possibly a single redox mediator have been described, more than one enzyme and / or more than one redox mediator can be linked to the same conductive film. .
  • the blocks described herein may be coated with a semipermeable membrane to pass reagents of a reaction and not pass other heavier elements such as chains of a linear polymer, enzymes and nanotubes of carbon.
  • the membrane is made of a biocompatible material, for example in chitosan, or in the material designated by the Dacron brand.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Sustainable Energy (AREA)
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  • Physics & Mathematics (AREA)
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  • Analytical Chemistry (AREA)
  • General Physics & Mathematics (AREA)
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  • Inert Electrodes (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

The invention relates to an electrochemical reactor block comprising at least two pellets (37) cut out of a flexible conductive film comprising chains of a linear polymer, carbon nanotubes being bound to each of said chains by pi-pi interaction, a catalyst agent selected from the group comprising enzymes, metal catalysts, macrocyclic catalysts and redox mediators being trapped between the pellets.

Description

BLOC DE REACTEUR ELECTROCHIMIQUE  ELECTROCHEMICAL REACTOR BLOCK
La présente demande de brevet revendique la priorité de la demande de brevet français FR15/59069 qui sera considérée comme faisant partie intégrante de la présente description. The present patent application claims the priority of the French patent application FR15 / 59069 which will be considered as an integral part of the present description.
Domaine Field
La présente invention concerne un procédé de fabrication d'un bloc d'un réacteur électrochimique au niveau duquel est susceptible de se produire une réaction entre des agents catalyseurs confinés dans ce réacteur et des composés présents dans un milieu liquide dans lequel baigne le réacteur. Cette réaction peut par exemple conduire à une déformation du réacteur, à la génération d'un potentiel électrique, ou à la transformation chimique du composé interagissant avec le réacteur. Ce réacteur peut être un bioréacteur.  The present invention relates to a method of manufacturing a block of an electrochemical reactor at which a reaction between catalytic agents confined in this reactor and compounds present in a liquid medium in which the reactor bathes is likely to occur. This reaction may for example lead to a deformation of the reactor, to the generation of an electrical potential, or to the chemical transformation of the compound interacting with the reactor. This reactor can be a bioreactor.
Un bioréacteur conduisant à la génération d'un potentiel électrique peut constituer une bioélectrode d'une biopile ou d'un biocapteur, de type à sucre-oxygène, par exemple à glucose- oxygène .  A bioreactor leading to the generation of an electrical potential may constitute a bioelectrode of a biopile or a biosensor, of the sugar-oxygen type, for example glucose-oxygen.
Un bioréacteur conduisant à la transformation chimique d'un composé interagissant avec le bioréacteur constitue par exemple un destructeur de glucose (glucose killer) en transformant par exemple du glucose en un composé qui sera par exemple éliminé par l'organisme dans lequel le bioréacteur est implanté. Bien que l'invention et l'état de la technique soient décrits ici principalement dans le cas de bioélectrodes on comprendra que l'invention s'applique à tout réacteur électrochimique, et pas seulement à un bioréacteur implantable in vivo. Exposé de l'art antérieur A bioreactor leading to the chemical transformation of a compound interacting with the bioreactor constitutes, for example, a glucose killer by transforming, for example, glucose into a compound that will be eliminated, for example, by the organism in which the bioreactor is implanted. . Although the invention and the state of the art are described here mainly in the case of bioelectrodes it will be understood that the invention is applicable to any electrochemical reactor, and not only to an implantable bioreactor in vivo. Presentation of the prior art
Divers types de bioélectrodes solides sont décrits dans l'art antérieur. Par exemple, le brevet français déposé sous le numéro N°10/52657 (B10272) décrit une pastille d'électrode obtenue par compression d'un matériau électriquement conducteur tel que du graphite, une enzyme, un médiateur rédox et éventuellement un polymère électriquement conducteur. La pastille a la forme d'un disque dont l'épaisseur est supérieure à 0,5 mm et dont le diamètre est supérieur à 0,5 cm. Bien qu'une telle pastille puisse être utilisée comme bioélectrode, sa rigidité et son encombrement limitent son utilisation notamment dans des parties du corps présentant des volumes réduits, par exemple dans un vaisseau sanguin .  Various types of solid bioelectrodes are described in the prior art. For example, the French patent filed under number 10/52657 (B10272) describes an electrode pad obtained by compression of an electrically conductive material such as graphite, an enzyme, a redox mediator and optionally an electrically conductive polymer. . The pellet is in the form of a disk whose thickness is greater than 0.5 mm and whose diameter is greater than 0.5 cm. Although such a pellet can be used as a bioelectrode, its rigidity and bulk limit its use especially in body parts with reduced volumes, for example in a blood vessel.
La demande de brevet français déposée sous le numéro 10/56672 (B10419) décrit une pastille d'électrode obtenue par compression d'un mélange en solution comprenant des nanotubes de carbone et une enzyme.  The French patent application filed under number 10/56672 (B10419) describes an electrode pad obtained by compression of a solution mixture comprising carbon nanotubes and an enzyme.
L'article "Plasma functionalization of bucky paper and its composite with phenylethynyl-terminated polyimide" de Qian Jiang et. al. paru en Février 2013 dans le volume 45 de la revue "Composites Part B: Engineering", décrit la fabrication d'un film conducteur composite de nanotubes de carbone et d'un polyimide.  The article "Plasma functionalization of bucky paper and its composite with phenylethynyl-terminated polyimide" by Qian Jiang and. al. published in February 2013 in volume 45 of the journal "Composites Part B: Engineering", describes the manufacture of a composite conductive film of carbon nanotubes and a polyimide.
Ces divers réacteurs présentent des inconvénients et notamment une durée de vie limitée.  These various reactors have disadvantages and in particular a limited life.
Il est souhaitable de prévoir un réacteur électro- chimique palliant au moins certains de ces inconvénients.  It is desirable to provide an electrochemical reactor that overcomes at least some of these disadvantages.
Résumé  summary
Ainsi, un mode de réalisation prévoit un procédé de fabrication d'un bloc de réacteur électrochimique comprenant les étapes suivantes : réaliser un film conducteur souple comprenant des chaînes d'un polymère linéaire à chacune desquelles sont liés par interaction pi-pi des nanotubes de carbone ; Thus, an embodiment provides a method of manufacturing an electrochemical reactor block comprising the following steps: producing a flexible conductive film comprising chains of a linear polymer to each of which are bonded by pi-pi interaction of carbon nanotubes;
découper des pastilles dans ledit film ; et  cutting pellets in said film; and
empiler les pastilles et les soumettre à une pression de l'ordre de 5 à 10 tonnes par centimètre carré en présence d'eau et d'un agent catalyseur.  stack the pellets and subject them to a pressure of the order of 5 to 10 tons per square centimeter in the presence of water and a catalyst.
Selon un mode de réalisation, l'étape de réalisation d'un film conducteur souple comprend les étapes suivantes :  According to one embodiment, the step of producing a flexible conductive film comprises the following steps:
préparer une suspension comprenant des nanotubes de carbone et des chaînes d'un polymère linéaire, chacune desdites chaînes portant une succession de groupements fonctionnels dont certains au moins comportent des groupements pi conjugués ; et filtrer sous vide la suspension pour obtenir un film desdites chaînes auxquelles sont liés les nanotubes de carbone par interaction pi-pi.  preparing a suspension comprising carbon nanotubes and chains of a linear polymer, each of said chains bearing a succession of functional groups, at least some of which contain conjugated pi groups; and vacuum-filtering the suspension to obtain a film of said chains to which the carbon nanotubes are bonded by pi-pi interaction.
Selon un mode de réalisation, l'agent catalyseur est choisi dans le groupe comprenant des enzymes, des catalyseurs métalliques, des catalyseurs macrocycliques et des médiateurs rédox.  In one embodiment, the catalyst is selected from the group consisting of enzymes, metal catalysts, macrocyclic catalysts, and redox mediators.
Selon un mode de réalisation, le polymère linéaire est choisi dans le groupe comprenant les polynorbornènes, le polyvinylpyrrolidone et le polystyrène sulfonate de sodium.  According to one embodiment, the linear polymer is chosen from the group comprising polynorbornenes, polyvinylpyrrolidone and sodium polystyrene sulphonate.
Selon un mode de réalisation, chacun desdits groupements fonctionnels comportant un groupement pi conjugué est choisi dans le groupe comprenant les porphyrines, la phthalocyanine, le pyrène, le benzène, l'indole, l'azulène, les phénothiazines et le naphtalène .  According to one embodiment, each of said functional groups comprising a conjugated pi group is chosen from the group comprising porphyrins, phthalocyanine, pyrene, benzene, indole, azulene, phenothiazines and naphthalene.
Selon un mode de réalisation, une distance inférieure à la longueur des nanotubes sépare deux groupements pi conjugués successifs d'une même chaîne de polymère linéaire.  According to one embodiment, a distance smaller than the length of the nanotubes separates two successive conjugated pi groups from the same linear polymer chain.
Selon un mode de réalisation, la longueur de chacune desdites chaînes de polymère est supérieure à 0,1 ym.  According to one embodiment, the length of each of said polymer chains is greater than 0.1 μm.
Un mode de réalisation prévoit un bloc de réacteur électrochimique comprenant au moins deux pastilles découpées dans un film conducteur souple comportant des chaînes d'un polymère linéaire à chacune desquelles sont liés par interaction pi-pi des nanotubes de carbone, un agent catalyseur choisi dans le groupe comprenant des enzymes, des catalyseurs métalliques, des cataly- seurs macrocycliques et des médiateurs rédox étant piégé entre les pastilles. One embodiment provides an electrochemical reactor block comprising at least two pellets cut from a flexible conductive film comprising chains of a linear polymer each of which is bonded by pi-pi interaction of carbon nanotubes, a catalyst selected from the group consisting of enzymes, metal catalysts, macrocyclic catalysts and mediators redox being trapped between the pellets.
Selon un mode de réalisation, le bloc de réacteur électrochimique constitue la cathode d'une biopile destinée à être immergée dans un milieu liquide contenant un sucre et de l'oxygène, et l'agent catalyseur est de la laccase.  According to one embodiment, the electrochemical reactor block constitutes the cathode of a biopile intended to be immersed in a liquid medium containing a sugar and oxygen, and the catalyst is laccase.
Selon un mode de réalisation, le bloc de réacteur électrochimique constitue l'anode d'une biopile destinée à être immergée dans un milieu liquide contenant un sucre et de l'oxygène, et l'agent catalyseur est de la glucose oxydase.  According to one embodiment, the electrochemical reactor block constitutes the anode of a biopile intended to be immersed in a liquid medium containing a sugar and oxygen, and the catalyst agent is glucose oxidase.
Brève description des dessins Brief description of the drawings
Ces caractéristiques et avantages, ainsi que d'autres, seront exposés en détail dans la description suivante de modes de réalisation particuliers faite à titre non limitatif en relation avec les figures jointes parmi lesquelles :  These and other features and advantages will be set forth in detail in the following description of particular embodiments in a non-limiting manner with reference to the accompanying drawings in which:
les figures 1A à 1C illustrent schématiquement des étapes d'un mode de réalisation d'un procédé de fabrication d'un film conducteur souple ;  FIGS. 1A to 1C schematically illustrate steps of an embodiment of a method of manufacturing a flexible conductive film;
la figure 2 illustre schématiquement la structure d'un film conducteur souple réalisé selon le procédé des figures 1A à 1C ;  FIG. 2 schematically illustrates the structure of a flexible conductive film made according to the method of FIGS. 1A to 1C;
la figure 3 représente à nouveau le film de la figure Figure 3 shows again the film of the figure
1C ; et 1 C ; and
la figure 4 représente un mode de réalisation d'un empilement de pastilles découpées dans un film.  Figure 4 shows an embodiment of a stack of pellets cut in a film.
Description détaillée detailed description
De mêmes éléments ont été désignés par de mêmes réfé¬ rences aux différentes figures et, de plus, les diverses figures ne sont pas tracées à l'échelle. Par souci de clarté, seuls les éléments qui sont utiles à la compréhension des modes de réalisa- tion décrits ont été représentés et sont détaillés. Les figures 1A à 1C illustrent schématiquement des étapes successives d'un mode de réalisation d'un film conducteur souple . The same elements have been designated with the same refe ¬ ences in the different drawings and, further, the various drawings are not drawn to scale. For the sake of clarity, only the elements that are useful for understanding the described embodiments have been shown and are detailed. FIGS. 1A to 1C schematically illustrate successive steps of an embodiment of a flexible conductive film.
A l'étape représentée en figure 1A, on a préparé une suspension 20 comprenant, dans un solvant 22, des nanotubes de carbone 24 et des chaînes 26 d'un polymère linéaire. De préfé¬ rence, le solvant 22 est hydrophobe. Le solvant peut être choisi dans le groupe comprenant le diméthylformamide (DMF) , le tétra- hydrofurane (THF) , le N-méthyl-2-pyrrolidone (NMP) , le diméthyl sulfoxide (DMSO) , le dichlorométhane, le nitrobenzène et le chloroforme. Chaque chaîne 26 du polymère linéaire porte une succession de groupements fonctionnels 28 comportant des groupe¬ ments pi conjugués 30. Les nanotubes de carbone 24 sont conducteurs en raison de la mobilité des électrons des groupements pi conjugués des nanotubes de carbone. Ainsi, un groupement pi conjugué 30 d'une chaîne 26 du polymère linéaire peut se lier par interaction pi-pi ( "pi-stacking" en anglais) à un groupement pi conjugué d'un nanotube de carbone 24. In the step shown in FIG. 1A, a suspension comprising, in a solvent 22, carbon nanotubes 24 and chains 26 of a linear polymer was prepared. Pref ¬ of No., the solvent 22 is hydrophobic. The solvent may be chosen from the group comprising dimethylformamide (DMF), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dichloromethane, nitrobenzene and chloroform. . Each channel 26 of the linear polymer carries a succession of functional groups 28 having group ¬ ments conjugated pi 30. The carbon nanotubes 24 are conductive because of the electron mobility of the moieties conjugated pi carbon nanotubes. Thus, a conjugated pi group of a chain 26 of the linear polymer can bind pi-pi interaction (pi-stacking) to a conjugated pi moiety of a carbon nanotube 24.
Les nanotubes de carbone 24 sont des nanotubes mono- feuillet ou multi-feuillets et peuvent avoir une longueur comprise entre 100 nm et 5 ym. Chaque groupement fonctionnel 28 comportant un groupement pi conjugué 30 est par exemple un macrocycle tel que les porphyrines et la phthalocyanine, ou un composé aromatique tel que du pyrène, du benzène, de l'indole, de l'azulène, des phénothiazines ou du naphtalène. Le polymère linéaire peut être choisi dans le groupe comprenant les polynorbornènes, le poly- vinylpyrrolidone (PVP) et le polystyrène sulfonate de sodium (PSS) . De préférence, la distance entre deux groupements pi conjugués 30 successifs d'une même chaîne 26 est inférieure à la longueur des nanotubes de carbone 24. Cette distance est par exemple comprise entre 5 et 50 nm pour des nanotubes d'une longueur de 200 à 500 nm. La longueur des chaînes 26 du polymère linéaire est choisie pour porter plusieurs groupements fonctionnels 28, par exemple au moins trois groupements fonctionnels 28, et de préférence au moins cinquante groupements fonctionnels 28. La longueur d'une chaîne peut être supérieure à 0,1 ym, de préférence supérieure à 10 ym. Le poids de l'ensemble des nanotubes de carbone 24 dans la suspension 20 est par exemple de 0,1 à 10 fois, de préférence 3 à 6 fois le poids de l'ensemble des chaînes 26 du polymère linéaire. The carbon nanotubes 24 are single or multi-layer nanotubes and may have a length of between 100 nm and 5 μm. Each functional group 28 comprising a conjugated pi group 30 is for example a macrocycle such as porphyrins and phthalocyanine, or an aromatic compound such as pyrene, benzene, indole, azulene, phenothiazines or naphthalene. . The linear polymer may be selected from the group consisting of polynorbornenes, polyvinylpyrrolidone (PVP) and sodium polystyrene sulfonate (PSS). Preferably, the distance between two successive conjugated pi groups of the same chain 26 is less than the length of the carbon nanotubes 24. This distance is for example between 5 and 50 nm for nanotubes with a length of 200 to 500 nm. The length of the chains 26 of the linear polymer is chosen to carry a plurality of functional groups 28, for example at least three functional groups 28, and preferably at least 50 groups. The length of a chain may be greater than 0.1 μm, preferably greater than 10 μm. The weight of all the carbon nanotubes 24 in the suspension 20 is, for example, from 0.1 to 10 times, preferably 3 to 6 times the weight of all the chains 26 of the linear polymer.
A l'étape illustrée en figure 1B, la suspension 20 est filtrée sous vide à travers une membrane 32, par exemple une membrane en PTFE (PolyTétraFluoroEthylène) , comprenant des pores 34 dont le diamètre est par exemple compris entre 0,1 et 0,5 ym. Les chaînes 26 du polymère linéaire auxquelles sont liés des nanotubes de carbone 24 s'accumulent alors en un film à la surface de la membrane 32.  In the step illustrated in FIG. 1B, the suspension 20 is vacuum filtered through a membrane 32, for example a PTFE (PolyTetrafluoroethylene) membrane, comprising pores 34 whose diameter is for example between 0.1 and 0, 5 ym. The chains 26 of the linear polymer to which carbon nanotubes 24 are bonded then accumulate in a film on the surface of the membrane 32.
Comme cela est illustré en figure 1C, après que le film a été séparé de la membrane 32, on obtient un film 36 comprenant des nanotubes de carbone liés aux chaînes de polymère linéaire. A titre d'exemple, l'épaisseur du film 36 est comprise entre 0,01 et 1 mm. La concentration surfacique de nanotubes de carbone peut être de 3,4 mg/cm2 et celle des chaînes du polymère linéaire peut être de 0,56 mg/cm2.  As illustrated in FIG. 1C, after the film has been separated from the membrane 32, a film 36 is obtained comprising carbon nanotubes bonded to the linear polymer chains. By way of example, the thickness of the film 36 is between 0.01 and 1 mm. The surface concentration of carbon nanotubes may be 3.4 mg / cm 2 and that of the linear polymer chains may be 0.56 mg / cm 2.
La figure 2 est une représentation imagée des chaînes FIG. 2 is a pictorial representation of the chains
26 de polymère linéaire liées à des nanotubes de carbone 24 dans le film 36. Les nanotubes de carbone 24 sont liés par interaction pi-pi avec des groupements pi conjugués 30 des groupements fonctionnels 28 portés par les chaînes 26 du polymère linéaire. Une chaîne 26 porte plusieurs nanotubes 24 et chaque nanotube peut être lié à plusieurs chaînes. The carbon nanotubes 24 are linked by pi-pi interaction with conjugated pI groups of the functional groups 28 carried by the chains 26 of the linear polymer. A chain 26 carries several nanotubes 24 and each nanotube can be linked to several chains.
Les nanotubes de carbone 24 du film 36 sont en contact les uns avec les autres ce qui entraîne que le film 36 est élec¬ triquement conducteur. Du fait que les chaînes 26 du polymère linéaire peuvent se déformer sous l'effet de contraintes mécaniques, le film 36 obtenu est souple. En particulier, les inventeurs ont constaté qu'un tel film conducteur souple pouvait être enroulé sur lui-même sans se casser. La figure 3 représente à nouveau le film conducteur souple obtenu par les étapes décrites précédemment en relation avec les figures 1A à 1C. The carbon nanotubes 24 of the film 36 are in contact with each other which causes the film 36 is elec trically conductive ¬. Because the chains 26 of the linear polymer can deform under the effect of mechanical stresses, the resulting film 36 is flexible. In particular, the inventors have found that such a flexible conductive film can be wound on itself without breaking. Figure 3 again shows the flexible conductive film obtained by the steps described above in connection with Figures 1A to 1C.
On propose ici de découper dans ce film, qui a par exemple un diamètre de l'ordre de 10 à 50 centimètres et une épaisseur de l'ordre de 100 à 300 ym, des pastilles 37. Ensuite, on réalise un bloc de réacteur 40 en empilant plusieurs de ces pastilles, par exemple trois dans l'exemple représenté, et en les soumettant à une pression, par exemple de l'ordre de 5 à 10 tonnes par centimètre carré. On obtient alors un bloc extrêmement rigide, à condition d'avoir réalisé la mise sous pression tandis que quelques gouttes d'eau sont insérées entre chaque pastille, et entre chaque pastille et les plaques d'appui de la presse. Alors, le bloc se détache facilement de la presse et ne s'arrache ni se délite. Cette solidité est attribuée à l'interaction entre les liaisons pi-pi du polymère d'une pastille et les nanotubes de carbone de la pastille adjacente.  It is proposed here to cut into this film, which has for example a diameter of the order of 10 to 50 centimeters and a thickness of the order of 100 to 300 μm, pellets 37. Then, a reactor block 40 is produced. by stacking several of these pellets, for example three in the example shown, and subjecting them to a pressure, for example of the order of 5 to 10 tons per square centimeter. An extremely rigid block is then obtained, provided that the pressurization has been carried out while a few drops of water are inserted between each pellet, and between each pellet and the pressing plates of the press. Then, the block is easily detached from the press and does not tear or disintegrate. This strength is attributed to the interaction between the pi-pi bonds of the polymer of a pellet and the carbon nanotubes of the adjacent pellet.
Ce bloc est fonctionnalisé en insérant entre les pastilles lors de la mise sous pression une solution aqueuse contenant un agent catalyseur adapté.  This block is functionalized by inserting between the pellets during the pressurization an aqueous solution containing a suitable catalyst.
Ainsi, l'agent catalyseur adapté est emprisonné (piégé) entre les pastilles et on obtient un bloc rigide peu susceptible de se déliter et dont l'agent catalyseur est immobilisé et non susceptible de s'échapper dans la solution dans laquelle le bloc est disposé en fonctionnement. La compression permet de faire la liaison entre les disques et par la même occasion, cette compres¬ sion et les liaisons pi-pi entre disques qui en résultent permettent d'emprisonner les agents catalyseurs placés entre les disques. Il peut en outre s'établir une liaison covalente ou non- covalente entre ces agents catalyseurs et les disques ce qui améliore encore le piégeage des agents catalyseurs. Thus, the suitable catalyst agent is trapped (trapped) between the pellets and a rigid block is obtained which is unlikely to disintegrate and the catalyst agent is immobilized and not likely to escape into the solution in which the block is disposed. Operating. Compression allows for liaising between the disks and the same time, this compres ¬ sion and pi-pi bonds between disks resulting catalysts allow imprisoning agents placed between the discs. It may further establish a covalent or non-covalent bond between these catalysts and the discs which further improves the trapping of the catalyst agents.
Les agents catalyseurs intercalés peuvent être des enzymes et/ou des médiateurs rédox, des catalyseurs métalliques ou macrocycliques ou des nanoparticules métalliques, des oxydes ou des complexes organométalliques . Tous ces composés catalysent une réaction et donc on a réalisé un réacteur et, s'il y a une réaction électrochimique, c'est un réacteur électrochimique. The intercalated catalyst agents may be enzymes and / or redox mediators, metal or macrocyclic catalysts or metal nanoparticles, oxides or organometallic complexes. All these compounds catalyze a reaction and thus a reactor was realized and, if there is an electrochemical reaction, it is an electrochemical reactor.
Dans le cas où l'agent catalyseur est une enzyme, pour améliorer son piégeage, les chaînes du polymère linéaire peuvent porter des groupements fonctionnels aptes à se lier à une enzyme en plus des groupements fonctionnels comprenant des groupements pi conjugués. A titre d'exemple, dans le cas où l'enzyme est conjugué à une avidine, le groupement fonctionnel peut être une biotine. A titre d'autre exemple, le groupement fonctionnel peut être un N-hydroxysuccinimide qui réagit avec les groupements amino des enzymes, créant ainsi une liaison covalente entre le film et l'enzyme. Dans une variante de réalisation, on peut prévoir d'utiliser des molécules bifonctionnelles dont chacune porte d'une part un groupement fonctionnel comportant un groupement pi conjugué apte à se lier à un élément du film conducteur souple, et d'autre part un groupement fonctionnel apte à se lier à une enzyme .  In the case where the catalyst is an enzyme, to improve its entrapment, the chains of the linear polymer may carry functional groups capable of binding to an enzyme in addition to functional groups comprising conjugated pi groups. By way of example, in the case where the enzyme is conjugated to an avidin, the functional group may be a biotin. As another example, the functional group may be an N-hydroxysuccinimide which reacts with the amino groups of the enzymes, thereby creating a covalent bond between the film and the enzyme. In an alternative embodiment, provision may be made to use bifunctional molecules, each of which bears, on the one hand, a functional group comprising a conjugated pi group capable of binding to a flexible conductive film element, and, on the other hand, a functional group. able to bind to an enzyme.
De la même manière, si l'agent catalyseur à immobiliser par piégeage doit être associé pour son fonctionnement à un médiateur rédox, on peut spécialiser le film avec des groupements fonctionnels aptes à se lier à un médiateur d' oxydo-réduction. Dans ce cas, on prévoit que les chaînes du polymère linéaire portent des groupements fonctionnels aptes à se lier au médiateur d' oxydo-réduction. On pourra également prévoir que les groupements fonctionnels aptes à se lier au médiateur d' oxydo-réduction soient portés par des molécules bifonctionnelles, ayant d'une part un groupement fonctionnel permettant de se lier au médiateur rédox et d'autre part un groupement pi-conjugué permettant la liaison avec les nanotubes de carbone ou que le médiateur d'oxydo- réduction soit fonctionnalisé par un groupement fonctionnel apte à se fixer directement sur les nanotubes de carbone. A titre d'exemple, dans le cas où le médiateur d' oxydo-réduction est le bleu de toluidine, ou chlorhydrate de triméthylthionine, on prévoit que le film comprend des groupements fonctionnels compor- tant des esters activés tel que le N-hydroxysuccinimide réagissant avec le motif amino du bleu de toluidine. Le médiateur d'oxydo- réduction peut également être le viologène, dans ce cas on prévoit de fonctionnaliser le viologène par un groupement pi conjugué tel qu'un pyrène, le viologène sera alors fixé au film par interaction pi-pi entre un nanotube de carbone et le groupement pi conjugué du viologène fonctionnalisé. Similarly, if the catalyst to be immobilized by trapping is to be associated for its operation with a redox mediator, the film can be specialized with functional groups capable of binding to an oxidation-reduction mediator. In this case, it is expected that the chains of the linear polymer carry functional groups capable of binding to the redox mediator. It will also be possible for the functional groups capable of binding to the redox mediator to be carried by bifunctional molecules, having on the one hand a functional group making it possible to bind to the redox mediator and on the other hand a pivotal group. conjugate allowing the binding with the carbon nanotubes or that the oxidation-reduction mediator is functionalized by a functional group capable of binding directly on the carbon nanotubes. For example, in the case where the redox mediator is toluidine blue or trimethylthionine hydrochloride, it is expected that the film comprises functional groups comprising activated esters such as the reactive N-hydroxysuccinimide with the amino motif of toluidine blue. The oxidation-reduction mediator can also be viologen, in which case viologen is expected to be functionalized by a pi-conjugated group such as pyrene, the viologen will then be attached to the film by pi-pi interaction between a carbon nanotube. and the conjugated pi moiety of the functionalized viologen.
Les exemples 1 à 4 ci-dessous sont des exemples de réacteurs électrochimiques comprenant des agents catalyseurs piégés entre des films de polymères linéaires et de nanotubes de carbone .  Examples 1 to 4 below are examples of electrochemical reactors comprising catalyst agents trapped between linear polymer films and carbon nanotubes.
Exemple 1 Example 1
L'agent catalyseur piégé entre les pastilles est une enzyme telle qu'une laccase. Le système, une fois immergé dans une solution aqueuse, par exemple dans un corps humain ou animal, fonctionne comme une cathode et un potentiel positif apparaît sur un contact formé sur une pastille supérieure.  The catalyst agent trapped between the pellets is an enzyme such as laccase. The system, once immersed in an aqueous solution, for example in a human or animal body, functions as a cathode and a positive potential appears on a contact formed on an upper pellet.
Exemple 2 Example 2
On réalise une biopile en utilisant un bloc d'anode et un bloc de cathode. L'agent catalyseur du bloc d'anode comprend par exemple de la glucose oxydase plus un médiateur redox et 1 ' agent catalyseur du bloc de cathode comprend par exemple de la laccase. Cette biopile est de faible encombrement et est implan- table in vivo.  A biopile is made using an anode block and a cathode block. The anode block catalyst comprises, for example, glucose oxidase plus a redox mediator and the catalyst of the cathode block comprises, for example, laccase. This biopile is small in size and is implantable in vivo.
Exemple 3 Example 3
Pour réaliser une pile, on peut aussi piéger au niveau d'un premier bloc de la porphyrine de rhodium et au niveau d'un deuxième bloc de la phthalocyanine de cobalt. La porphyrine de rhodium agit pour oxyder du glucose et la phthalocyanine de cobalt pour réduire l'oxygène. On notera que cette réaction ne fonctionne que quand les deux blocs sont immergés dans une solution à pH élevé, ce qui constitue une pile non implantable in vivo.  To make a stack, one can also trap at a first block of the rhodium porphyrin and at a second block of cobalt phthalocyanine. Rhodium porphyrin acts to oxidize glucose and cobalt phthalocyanine to reduce oxygen. It should be noted that this reaction only works when the two blocks are immersed in a high pH solution, which constitutes a non-implantable cell in vivo.
Exemple 4 Example 4
Le catalyseur inséré entre les pastilles est constitué de nanoparticules de platine. Quand le système est immergé en milieu acide dans un électrolyseur et qu'un courant est amené à circuler à travers le bloc entre un contact formé sur une pastille supérieure et une électrode immergée dans le bain de l'électro- lyseur, le système fonctionne pour catalyser la réaction de production d'hydrogène. The catalyst inserted between the pellets consists of platinum nanoparticles. When the system is immersed in an acidic medium in an electrolyser and a current is brought to flow through the block between a contact formed on an upper pellet and an electrode immersed in the bath of the electrolyser, the system functions to catalyze the hydrogen production reaction.
De façon générale, quels que soient les éléments de catalyseur utilisés, on obtiendra un bon piégeage des éléments catalyseurs et donc une grande durée de vie du dispositif.  In general, whatever the catalyst elements used, a good trapping of the catalyst elements will be obtained and thus a long service life of the device.
VARIANTES VARIATIONS
Des modes de réalisation particuliers ont été décrits. Diverses variantes et modifications apparaîtront à l'homme de l'art. En particulier, les blocs décrits ci-dessus peuvent être fonctionnalisés par d'autres composés, par d'autres enzymes, et par d'autres médiateurs d' oxydo-réduction que ceux indiqués à titre d'exemple dans la présente description.  Particular embodiments have been described. Various variations and modifications will be apparent to those skilled in the art. In particular, the blocks described above may be functionalized by other compounds, other enzymes, and other redox mediators than those exemplified herein.
Bien que l'on ait décrit des blocs comprenant une seule enzyme et éventuellement un seul médiateur d' oxydo-réduction, plus d'une enzyme et/ou plus d'un médiateur d' oxydo-réduction peuvent être liés à un même film conducteur.  Although blocks comprising a single enzyme and possibly a single redox mediator have been described, more than one enzyme and / or more than one redox mediator can be linked to the same conductive film. .
Les blocs décrits ici peuvent être revêtus d'une membrane semi-perméable pour laisser passer les réactifs d'une réaction et ne pas laisser passer d'autres éléments plus lourds tels que des chaînes d'un polymère linéaire, des enzymes et des nanotubes de carbone. Dans le cas où ces blocs constituent un bioréacteur destiné à être implanté in-vivo, la membrane est en un matériau biocompatible, par exemple en chitosane, ou en le matériau désigné par la marque Dacron.  The blocks described herein may be coated with a semipermeable membrane to pass reagents of a reaction and not pass other heavier elements such as chains of a linear polymer, enzymes and nanotubes of carbon. In the case where these blocks constitute a bioreactor intended to be implanted in vivo, the membrane is made of a biocompatible material, for example in chitosan, or in the material designated by the Dacron brand.

Claims

REVENDICATIONS
1. Procédé de fabrication d'un bloc de réacteur électrochimique comprenant les étapes suivantes : A method of manufacturing an electrochemical reactor block comprising the steps of:
réaliser un film conducteur souple (36) comprenant des chaînes d'un polymère linéaire à chacune desquelles sont liés par interaction pi-pi des nanotubes de carbone ;  producing a flexible conductive film (36) comprising chains of a linear polymer to each of which are bonded by pi-pi interaction of carbon nanotubes;
découper des pastilles (37) dans ledit film ; et empiler les pastilles et les soumettre à une pression de l'ordre de 5 à 10 tonnes par centimètre carré en présence d'eau et d'un agent catalyseur.  cutting pellets (37) into said film; and stacking the pellets and subjecting them to a pressure in the range of 5 to 10 tonnes per square centimeter in the presence of water and a catalyst.
2. Procédé selon la revendication 1, dans lequel l'étape de réalisation d'un film conducteur souple comprend les étapes suivantes :  2. Method according to claim 1, wherein the step of producing a flexible conductive film comprises the following steps:
préparer une suspension (20) comprenant des nanotubes de carbone (24) et des chaînes d'un polymère linéaire (26), chacune desdites chaînes portant une succession de groupements fonctionnels (28) dont certains au moins comportent des groupements pi conjugués ; et  preparing a suspension (20) comprising carbon nanotubes (24) and chains of a linear polymer (26), each of said chains carrying a succession of functional groups (28) at least some of which comprise conjugated pi groups; and
filtrer sous vide la suspension (20) pour obtenir un film (36) desdites chaînes (26) auxquelles sont liés les nanotubes de carbone (24) par interaction pi-pi.  vacuum filtering the suspension (20) to obtain a film (36) of said chains (26) to which the carbon nanotubes (24) are bonded by pi-pi interaction.
3. Procédé selon la revendication 1, dans lequel l'agent catalyseur est choisi dans le groupe comprenant des enzymes, des catalyseurs métalliques, des catalyseurs macro¬ cycliques et des médiateurs rédox. 3. The method of claim 1 wherein the catalyzing agent is selected from the group comprising enzymes, metal catalysts, macro catalysts ¬ cyclic and redox mediators.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le polymère linéaire est choisi dans le groupe comprenant les polynorbornènes, le polyvinylpyrrolidone et le polystyrène sulfonate de sodium.  4. The process according to any one of claims 1 to 3, wherein the linear polymer is selected from the group consisting of polynorbornenes, polyvinylpyrrolidone and sodium polystyrene sulfonate.
5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel chacun desdits groupements fonctionnels (28) comportant un groupement pi conjugué (30) est choisi dans le groupe comprenant les porphyrines, la phthalocyanine, le pyrène, le benzène, l'indole, l'azulène, les phénothiazines et le naphtalène . The process according to any one of claims 1 to 4, wherein each of said functional groups (28) having a pi conjugated group (30) is selected from the group consisting of porphyrins, phthalocyanine, pyrene, benzene, indole, azulene, phenothiazines and naphthalene.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel une distance inférieure à la longueur des nanotubes (24) sépare deux groupements pi conjugués (30) successifs d'une même chaîne de polymère linéaire (26). 6. A method according to any one of claims 1 to 5, wherein a distance less than the length of the nanotubes (24) separates two successive conjugated pi groups (30) of the same linear polymer chain (26).
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel la longueur de chacune desdites chaînes de polymère (26) est supérieure à 0,1 um.  The method of any one of claims 1 to 6, wherein the length of each of said polymer chains (26) is greater than 0.1 μm.
8. Bloc de réacteur électrochimique comprenant au moins deux pastilles (37) découpées dans un film conducteur souple (36) comportant des chaînes d'un polymère linéaire à chacune desquelles sont liés par interaction pi-pi des nanotubes de carbone, un agent catalyseur choisi dans le groupe comprenant des enzymes, des catalyseurs métalliques, des catalyseurs macrocycliques et des médiateurs rédox étant piégé entre les pastilles.  8. electrochemical reactor block comprising at least two pellets (37) cut from a flexible conductive film (36) comprising chains of a linear polymer to each of which are bonded by pi-pi interaction carbon nanotubes, a chosen catalyst agent in the group comprising enzymes, metal catalysts, macrocyclic catalysts and redox mediators being trapped between the pellets.
9. Bloc de réacteur électrochimique selon la revendi¬ cation 8, constituant la cathode d'une biopile destinée à être immergée dans un milieu liquide contenant un sucre et de l'oxygène, dans lequel ledit agent catalyseur est de la laccase. 9. Block electrochemical reactor according to revendi ¬ cation 8, constituting the cathode of a biofuel cell will be immersed in a liquid medium containing a sugar and oxygen, wherein said catalyzing agent is laccase.
10. Bloc de réacteur électrochimique selon la revendi¬ cation 8, constituant l'anode d'une biopile destinée à être immergée dans un milieu liquide contenant un sucre et de l'oxygène, dans lequel ledit agent catalyseur est de la glucose oxydase . 10. Block electrochemical reactor according to revendi ¬ cation 8, constituting the anode of a biofuel cell will be immersed in a liquid medium containing a sugar and oxygen, wherein said catalyzing agent is glucose oxidase.
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